US3376139A - Photosensitive prepolymer composition and method - Google Patents

Photosensitive prepolymer composition and method Download PDF

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Publication number
US3376139A
US3376139A US539236A US53923666A US3376139A US 3376139 A US3376139 A US 3376139A US 539236 A US539236 A US 539236A US 53923666 A US53923666 A US 53923666A US 3376139 A US3376139 A US 3376139A
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prepolymer
aryl
composition
methyl
diallyl
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Gilano Michael Nicholas
Irvin W Martenson
Lawrence H Ott
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Priority to US539236A priority Critical patent/US3376139A/en
Priority to US562691A priority patent/US3462267A/en
Priority to SE09726/67*A priority patent/SE340563B/xx
Priority to ES342356A priority patent/ES342356A1/es
Priority to CH951867A priority patent/CH484458A/de
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/117—Free radical

Definitions

  • the present invention relates to the photosensitization of prepolymer compositions, and more particularly to chemical compositions for making photographic relief images of particular use in the graphic arts, such as for printing plates, printed circuit boards, name plates, chemical milling, etc.
  • Bichromated shellac, chromated polyvinyl alcohols, and chromated polyvinyl butyrals have limited shelf life, and the bichromate sensitizer must be stored in a separate container and mixed with the film-forming polymer just prior to use.
  • Polyvinyl cinnamate and related unsaturated ester polymers undergo film shrinkage during overexposure to actinic light, and, therefore, have certain limitations for fine-detail work.
  • photosensitive compositions which are characterized by improved detail, better chemical resistance, long storage life, reproducibility from batch to batch, being preparable as a one-package system, and ease of removal after etching.
  • photosensitive film compositions which do not appreciably shrink when exposed to actinic rays and which can be repeatedly washed and etched as required without adverse effects to the image detail or undercutting of the relief image.
  • Another object of the present invention is to provide a photosensitive composition which can be easily removed by dipping in a solvent for several minutes and wiping it off.
  • Another object of the present invention is to provide a stable photosensitive composition which requires no blending, heating, or chemical treatment before use, which can be exposed to light rays over a Wide spectral range, and which permits metals and other objects to be precoated and stored for long periods before and after exposure.
  • Another object of the present invention is to provide a superior stable light-sensitive composition which can be cross linked under the influence of actinic rays and which will form a durable coating having good heat resistance,
  • a prepolymer of an aryl allyl ester having two or more allyl groups is combined 'with an initiator or sensitizing agent and dissolved in a suitable solvent.
  • aryl allyl ester is herein defined to include polynuclear allyl esters and aryl allyl ester copolymers, in addition to aryl allyl esters having only a single aryl group.
  • the sensitizing agent must be one that absorbs actinic radiation so as to dissociate into free radicals which accelerate complete polymerization of the prepolymer.
  • the sensitizing agent can be ethers of benzoin, such as methyl, ether of benzoin; p,p-substituted benzophenones such as 4,4'-bis(dimethylamine) benzophenone and 4,4'-bis(di ethylamine) benzophenone; or his l-anthraquinonyl amino anthraquinones such as 1,4 bis(1-anthraquinoyl amino) anthraquinone and 1,5 bis(l-anthraquinonyl amino) anthraquinone, and combinations thereof.
  • Other useful sensitizing agents include polynuclear quinones such as 1,2-benzanthraquinone and 2 methyl anthraquinone; mononuclear quinones such as 2,5-diphenyl-pquinone; aromatic a-diketones such as benzil; substituted aryl methylene dioxy compounds such as piperonal, piperoin, 3,4-methylene dioxychalcone, and 5,6-methylene dioxyhydrindone-l; substituted fi-naphthoselenazolines such as l-methyl-Z-acetyl methylene ,3 naphthoselenazoline; substituted B-benzothiazolines such as 3-methyl-2-benzoyl methylene benzothiazoline; substituted S-naphthothiazolines such as 1-methyl-2-menzoyl methylene-B-naphthothiazoline; anthrones such as anthrone; benzanthrones such as benz-Z
  • prepolymer an intermediate stage in the reaction of a thermosetting resin, which stage is similar to B-staged epoxy resins. That is, the prepolymer, which is soluble, is a monomer polymerized to partial completion.
  • the prepolymer of the present invention with a proper sensitizing agent, dissolving it in a suitable solvent, and eposing the combination to actinic radiation, the polymerization is completed to form a thermoset, irreversible, infusible, solid.
  • FIGURE 1 is an isometric view of a laminated metalclad board.
  • FIGURES 2-6 are sectional views taken through the board of FIGURE 1, and showing successive steps in the use of the photosensitive resist composition according to the present invention.
  • the prepolymers of aryl diallyl esters can be prepared by controlled partial polymerization of the monomeric aryl diallyl ester.
  • the diallyl isophthalate liquid monomer is converted to the prepolymer by heating the liquid daillyl isophthalate in a suitable solvent such as xylene in the presence of a peroxide catalyst, and by not allowing the polymerization to proceed to completion.
  • the polymerization is stopped when practically all the change in specific gravity has taken place, preferably to an iodine number of 56 to 58.
  • the reaction is stopped at this point by cooling and the addition of a hydroquinone inhibitor.
  • the prepolymer is then recovered from the solvent and is washed and dried, A white powdered resin is obtained which when dissolved in a suitable solvent yields a water-white solution.
  • the photosensitive resin composition can be a solid mixture of materials, as in a dried coating, or a solution of the materials in a suitable organic solvent or mixture of solvents.
  • Good solvents for the sensitized aryl allyl prepolymers include:
  • Esters such as isobutyl acetate, butyl carbitol acetate, amyl acetate, butyl cellosolve acetate, ethyl acetate, and methyl cellosolve acetate.
  • Ketones such as acetophenone, diacetone alcohol, diisobutyl ketone, methyl isobutyl ketone, and isophorone.
  • Glycol ethers such as ethylene glycol methyl ether, diethylene glycol methyl ether, and propylene glyco methyl ether.
  • Aromatic solvents such as benzene, toluene, and xylene.
  • Chlorinated solvents such as 1,1,1-trichlorethane, trichlorethylene, and methylene chloride.
  • the described prepolymer resin has the rare characteristic that its polymerization can be stopped at a determined point and it can be precipitated as a solid and stored for an indefinite period at ambient temperatures, and if desired, converted at any time into an infusible solid by employing peroxides and heat and pressure, or in accordance with this invention, by means of actinic radiation.
  • diallyl isophthalate prepolymer exhibits film-forming properties, excellent chemical resistance to 'both acids and alkalis, excellent moisture and heat resistance, and shows very little shrinkage when further cross-linked with actinic light. As a result of these properties, it is an ideal material for use as a resist in the manufacture of printed circuit boards and semiconductors, and in microchemical milling.
  • the light-sensitive polymeric composition by being preshrunk before use, makes it possible to obtain accurate dimensional detail in printed circuits, chemical milling, etc., since a minimum shrinkage will occur during the further cross-linking of the aryl allyl ester prepolymer when it is exposed to actinic rays. This is because of the fact that the aryl allyl ester prepolymers have been previously processed to the point where practically all of the change in specific gravity has taken place, thereby assuring that very little shrinkage will occur during exposure to actinic radiation. This means that for fine detail work, the shrinkage does not have to be compensated for in the photographic negative.
  • Another advantage is the fact that the prepolymer can be dissolved in a suitable organic solvent along with the sensitizers considerably in advance of exposure, and will exhibit excellent shelf life under non-ideal conditions of temperature.
  • the prepolymers of aryl diallyl, aryl triallyl, aryl tetra allyl and polynuclear dialyl esters exhibit excellent light sensitivity and can be sensitized to increase their reactivity to actinic rays as much as 100 to 200 times.
  • sensitizer compounds When sensitizer compounds are added to the prepolymeric aryl allyl esters, they exhibit exceptional stability, and therefore have long shelf life.
  • the concentration of sensitizer in the photo resist composition depends upon the amount of sensitive polymeric compound, i.e., the aryl allyl prepolymer, present.
  • the prepolymer of diallyl isophthalate from about 1 to 20%, preferably 1.5 percent by weight, of 1,4 bis(l-anthraquinoyl amino) anthraquinone can be used.
  • Some sensitizers such as p,p' substituted benzophenones, e.g., 4,4-bis(dimethylamino) benzophenone, in an amount less than 1.5%, cause a considerable increase in sensitivity to actinic light.
  • the sensitizer is excited by the actinic radiation, and, in turn, speeds up the polymerization. This is accomplished by the sensitizer being dissociated into free radicals by the actinic radiation or energy that it absorbs. The free radicals initiate the polymerization of the prepolymer.
  • Example I A typical resist formulation useful for making relief images on copper plates or printing plates is prepared as follows:
  • the aryl allyl prepolymers are interchangeable in the photo resist composition and can be sensitized by the same initiators.
  • diallyl isophthalate will be used, but it is. not
  • Example VIII elevated temperature in subdued light the plate is placed Grams in intimate contact with a photographic negative and Diallyl isophthalate prepolymer 1.5 exposed to actinic light.
  • Useful light sources are mercury Methyl isobutyl ketone 5.0 vapor lamps or high-ampere white-flame arcs. Exposure 1,2-benzanthraquirione 0.05 5 times vary from a fraction of a minute to several minutes at a distance of 2 to 3 feet, respectively.
  • the exposed Examp 16 IX Grams plate is then developed by immersion in an organic solvent Dianyl isophthalate Prepolymer 15 such as methyl ethyl ketone or 1,l,l-trichlorethane for Cellosolvg acetate 20 less than a minute at room temperature.
  • Dianyl isophthalate Prepolymer 15 such as methyl ethyl ketone or 1,l,l-trichlorethane for Cellosolvg acetate 20 less than a minute at room temperature.
  • theorganic solvent dissolves the unexposed areas of 2 th 1 th thes coating and allows the exposed areas to remain intact y an raqumone on the support plate.
  • the transparent image on the photo- Example X graphic negative is thus accurately reproduced as a resist Grams image on the support plate.
  • Diallyl isophthalate prepolymer 1.5 After development, an optional step is to dye the resist Methyl isobutyl ketone 2.0 image, which is normally transparent and colorless and Cellosolve acetate 2.0 difiicult to see, by immersion for less than a minute in a Toluene 1.0 dye bath comprising a synthetic dye in a compatible Piperonal 0.15 organic solvent. Finally, the plate is washed in flowing water and dried.
  • the resist image serves as an intermediate step for electroplating and Example XII evaporative-film operations, or as an opaque film for Grams images on transparent objects as signs, or to produce Diallyl isophthalate prepolymer 1.5 decorative effects.
  • photo milling which is a relatively Methyl isobutyl ketone 2.0 new method for making small accurate metal parts of Xylene 2.0 thin metal sheet
  • the resist image is applied to both sides Cellosolve acetate 1.0 of the sheet in accurate register.
  • the metal etchant i l-methyl-z-benloyl methylefle-fi-naphthothialoline then applied to both sides to remove unwanted metal.
  • FIGURE 1 The probable structure of the recurring units of the Turning f to the i f which illustrate the use prepolymers f aryl n esters can be better understood of the described photosensitive resist composition in a from the following example process for making printed circuit boards, FIGURE 1
  • Prepolymer of diallyl isophthalate shows a board 11 having a covering layer 12 of 0.0014 (CH-CH2OOC OCOOCH2(H3H IIs (E CH2 0oooHioH-oI-I-CHioO L H3 CH3 N
  • FIGURE 2 is a sectional view showing board 11 after I the described photosensitive resist composition is applied a -co0oH,-orr o as by flowing onto the surface of copper layer 12 to form a N layer 14. The excess resist can be drained by holding the 2 board vertically for several minutes.
  • the coating is then (3) Prepolymer of tetra-allyl pyromellitate dried by placing board 11 in an oven maintained at CH2 CH3 CH3 CH2 iiHCHi0oc -CoooHi0HoHoH0oC -ooooHi( iH CH-OHOOO COOCH2-CH HCCH2OOC- COOCH2CH Ha I H2 (3H2 (13H; N
  • FIGURE 3 shows how mask 15, which can be a photopolyrnerizable coating composition includes the following graphic negative of an electrical circuit, is placed in steps: the photosensitive material is applied to the support contact with the photosensitive layer 14. The combination plate by dipping, spraying, or roller coating. The wet is then put into the vacuum frame of a printing machine coated plate is commonly drained or whirled to obtain and exposed for one to three minutes to a 35-ampere a uniform film thickness. After drying at room or slightly white-flame are light source about 2 feet away, represented by arrows 21. Light of from 3200-4100 angstrom units is very satisfactory.
  • the board is removed and the coating developed by placing the board vertically in a tank of methyl ethyl ketone for approximately 30 seconds. The board is then removed and immersed for 30 seconds in a second tank containing a solution of dye in organic solvent to render the normallytransparent resist image visible.
  • FIGURE 4 shows the board after it is rinsed in flowing water to remove adhering dissolved resist solution and excess dye and finally dried by slightly warming it.
  • the board at this stage is ready for etching and his on the copper surface the image of the electrical circuit, this image being comprised of a film of dry, hard, polymerized resist.
  • the surface area other than that covered by the resist image is bare copper.
  • FIGURE 5 shows the board after the bare copper is removed by a suitable acid-type etchant.
  • the board can be placed in a spray-type etching machine, of a kind commonly used in the industry, which sprays a solution of ferric chloride on the surface.
  • the concentration of the ferric chloride commonly stated in terms of specific gravity, can be 38 degrees Baum.
  • Within several minutes the bare unprotected copper on the board surface will be completely etched away.
  • the board is then removed and thoroughly rinsed to remove all traces of ferric chloride, and then dried.
  • FIGURE 6 shows the board after it is immersed in a solvent such as trichlorethylene or methyl ethyl ketone to soften the resist image, which can be removed by scrubbing with a mild abrasive cleaner, revealing the brightcopper electrical circuit.
  • the finished circuit board can be rinsed in hot water and dried.
  • a photosensitive resist composition consisting essentially of:
  • composition as defined in claim 1 in which said prepolymer has been recovered from the reaction mixture produced by polymerization of monomer.
  • a composition as defined in claim 1 in which said prepolymer has been precipitated from the reaction mix-- I sensitizing agent is selected from the group consisting of methyl ether of benzoin, 4,4 bis(dimethylamino)benzophenone, 4,4 bis(diethylamino)benzophenone, 1,4 bis(1- anthraquinoyl amino) anthraquinone, 1,4, bis(1-anthra quinoyl amino) anthraquinone, 1,2 benzanthraquinone, 2 methyl anthraquinone, 2,5-diphenyl-p-quinone, benzil, piperonal, 3,4-methylene dioxychalcone, 5,6-methylene dioxhydrindone-l, piperoin, l-methyl-Z-acetyl methylene- ⁇ 3- naphthoselenazoline, 3-methyl-2-benzoyl methylene benz othiozoline, 1-methyl-2-benzoy
  • composition as defined in claim 2 in which said prepolymer is selected from the group consisting of aryl diallyl esters, aryl triallyl esters, aryl tetra allyl. esters, polynuclear polyallyl esters, and aryl polyallyl ester copolymers.
  • composition as defined in claim 2 in which said prepolymer is selected from the group consisting of diallyl isophthalate, diallyl terephthalate, diallyl anthralate, triallyl trimellitate and tetra allyl pyromellitate.
  • a method of photographically printing animage upon a surface consisting essentially of the steps of:
  • a photopolymerizablelayer comprising a photopolymerization sensitizing agent and a prepolymer selected from the group consisting of aryl diallyl esters, aryl triallyl esters, aryl tetra allyl esters, polynuclear polyallyl esters, and aryl polyallyl ester copolymers, said prepolymer being capable of polymerizing to completion by photoinitiated polymerization in the presence of said sensitizing agent which is activatable by actinic radiation, said prepolymer being a solvent-soluble material which is a solid at ambient temperature, has been recovered from the reaction mixture produced by polymerization of monomer and undergoes very little shrinkage when further cross-linked by actinic radiation,
  • substantially complete polymerization of said prepolymer occurs throughout the entire thickness of said layer in the areas thereof corresponding to said substantially transparent area, whereby said layer in said corresponding areas is converted to the thermoset, irreversible, infusible, solid state, but without any substantial polymerization in the areas of said layer corresponding to said substantially opaque areas, and r (d) removing said layer in the latter corresponding areas.
  • Photosensitive photographic means including a support surface having thereon a dry photopolymerizable layer consisting essentially of:
  • said prepolymer being capable 2,832,758 4/1958 Heiburger et al. 26078.4 of polymerizing to completion by photoinitiated po- 3,030,341 4/1962 Willard 260-78.4 lymerization in the presence of said sensitizing agent, 3,036,915 5/ 1962 Notley 96--115 XR and being a solvent-soluble material which is a solid 5 3,060,025 10/1962 Burg et al. 96116 XR at ambient temperature, has been recovered from the OTHER REFERENCES reaction mixture produced by polymerization of monomer and undergoes very little shrinkage When Nichols, and Flowers, IIld- & g

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
US539236A 1966-02-01 1966-02-01 Photosensitive prepolymer composition and method Expired - Lifetime US3376139A (en)

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Application Number Priority Date Filing Date Title
US539236A US3376139A (en) 1966-02-01 1966-02-01 Photosensitive prepolymer composition and method
US562691A US3462267A (en) 1966-02-01 1966-07-05 Offset printing plates
SE09726/67*A SE340563B (es) 1966-02-01 1967-04-29
ES342356A ES342356A1 (es) 1966-02-01 1967-06-27 Metodo de produccion de una placa de imprimir litografica presensibilizada.
CH951867A CH484458A (de) 1966-02-01 1967-07-05 Verfahren zur Herstellung von vorsensibilisierten lithographischen Druckplatten und Verwendung derselben

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US56269166A 1966-07-05 1966-07-05

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US3458313A (en) * 1966-09-07 1969-07-29 Nasa High resolution developing of photosensitive resists
US3462267A (en) * 1966-02-01 1969-08-19 Dynachem Corp Offset printing plates
US3475176A (en) * 1966-09-06 1969-10-28 Eastman Kodak Co Azide sensitized photosensitive prepolymer compositions
US3622365A (en) * 1968-04-18 1971-11-23 Fairchild Camera Instr Co Process of forming an arsenic sulfide mask
US3640765A (en) * 1969-08-06 1972-02-08 Rca Corp Selective deposition of metal
US3751248A (en) * 1971-12-27 1973-08-07 Bell Telephone Labor Inc Method of selective multilayered etching
US3808004A (en) * 1969-05-29 1974-04-30 Richardson Graphic Co Lithographic plate and photoresist having two photosensitive layers
US3883352A (en) * 1973-04-05 1975-05-13 Grace W R & Co Process for forming a photocured solder resist
US3905815A (en) * 1971-12-17 1975-09-16 Minnesota Mining & Mfg Photopolymerizable sheet material with diazo resin layer
US4133685A (en) * 1969-05-29 1979-01-09 Richardson Chemical Company Lithographic plate and photoresist having photosensitive layers of diazo and cinnamoylated polyvinyl alcohol materials
DE2950212A1 (de) * 1978-12-15 1980-06-19 Fujitsu Ltd Negative tiefultraviolette abdeckung und verfahren zum herstellen eines abdeckungsmusters
US4330611A (en) * 1969-05-29 1982-05-18 Richardson Graphics Company Lithographic plate and photoresist having photosensitive layers of diazo and cinnamoylated polyvinyl alcohol materials
DE3246403A1 (de) * 1982-12-15 1984-06-20 Merck Patent Gmbh, 6100 Darmstadt Verfahren zur entwicklung von reliefstrukturen auf der basis von strahlungsvernetzten polymervorstufen hochwaermebestaendiger polymere
US4486526A (en) * 1969-05-29 1984-12-04 Richardson Graphics Company Lithographic plate and photoresist having photosensitive layers of diazo and cinnamoylated phenol-blocked isocyanate polyurethane materials
US4687727A (en) * 1982-09-21 1987-08-18 Fuji Photo Film Co., Ltd. Light-sensitive planographic printing plate with layer of diazo resin containing photopolymerizable composition
EP0708369A1 (en) 1994-10-11 1996-04-24 Morton International, Inc. Solvent system for forming films of photoimageable compositions

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US3635711A (en) * 1969-06-06 1972-01-18 Grace W R & Co Method and automated apparatus for photocomposing
US3648607A (en) * 1969-08-21 1972-03-14 Xerox Corp Imaging system
CA980163A (en) * 1970-12-23 1975-12-23 Jack R. Celeste Photocrosslinkable compositions and elements containing heterocyclic nitrogen-containing compounds
US3673140A (en) * 1971-01-06 1972-06-27 Inmont Corp Actinic radiation curing compositions and method of coating and printing using same
US3772171A (en) * 1971-04-05 1973-11-13 Inmont Corp Novel quick setting inks
US3902902A (en) * 1971-06-22 1975-09-02 Siemens Ag Method of forming a photo-cross-linked insulator film
US3890149A (en) * 1973-05-02 1975-06-17 American Can Co Waterless diazo planographic printing plates with epoxy-silane in undercoat and/or overcoat layers
US4197125A (en) * 1974-02-12 1980-04-08 Teijin Limited Process of making photosensitive resin printing plates
DE2457882B2 (de) * 1974-12-06 1977-06-02 Siemens AG, 1000 Berlin und 8000 München Waermebestaendige, lichtvernetzbare massen
US4233390A (en) * 1979-07-20 1980-11-11 Polychrome Corporation Lithographic printing plate having dual photosensitive layering
US4292396A (en) * 1980-03-03 1981-09-29 Western Litho Plate & Supply Co. Method for improving the press life of a lithographic image having an outer layer comprising an epoxy resin and article produced by method
US4452877A (en) * 1982-08-26 1984-06-05 American Hoechst Corporation Electrolysis treatment of light sensitive diazo coated supports
US4785062A (en) * 1984-07-31 1988-11-15 W. R. Grace & Co.-Conn. Reaction product of O-epoxyalkylated tetrakis(hydroxyphenyl)ethane resin and phenol with product having no remaining epoxy groups
US4608331A (en) * 1984-11-16 1986-08-26 Witco Chemical Corporation Photosensitive plates with diazonium composition layer and polyurethane photopolymer with unsaturation in side chain overlayer
US4684599A (en) * 1986-07-14 1987-08-04 Eastman Kodak Company Photoresist compositions containing quinone sensitizer
US4886731A (en) * 1987-01-05 1989-12-12 Cookson Graphics Inc. Multilayer photopolymeric printing plates with photoreactive diazo compounds and photopolymerizable compositions
US5254429A (en) * 1990-12-14 1993-10-19 Anocoil Photopolymerizable coating composition and lithographic printing plate produced therefrom

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US2339058A (en) * 1942-03-25 1944-01-11 Gen Electric Coating composition comprising partially polymerized allyl esters containing polymerization inhibitor
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US3060025A (en) * 1959-11-03 1962-10-23 Du Pont Photopolymerization process of image reproduction

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US3376138A (en) * 1963-12-09 1968-04-02 Gilano Michael Nicholas Photosensitive prepolymer composition and method
US3376139A (en) * 1966-02-01 1968-04-02 Gilano Michael Nicholas Photosensitive prepolymer composition and method

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US2339058A (en) * 1942-03-25 1944-01-11 Gen Electric Coating composition comprising partially polymerized allyl esters containing polymerization inhibitor
US2791504A (en) * 1951-08-20 1957-05-07 Du Pont Photopolymerizable elements
US2722512A (en) * 1952-10-23 1955-11-01 Du Pont Photopolymerization process
US2832758A (en) * 1954-02-19 1958-04-29 Fmc Corp Solid prepolymers of diallyl phthalate
US3030341A (en) * 1959-05-06 1962-04-17 Fmc Corp Manufacture of prepolymers
US3060025A (en) * 1959-11-03 1962-10-23 Du Pont Photopolymerization process of image reproduction
US3036915A (en) * 1960-01-27 1962-05-29 Du Pont Photopolymerizable compositions and elements

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3462267A (en) * 1966-02-01 1969-08-19 Dynachem Corp Offset printing plates
US3475176A (en) * 1966-09-06 1969-10-28 Eastman Kodak Co Azide sensitized photosensitive prepolymer compositions
US3458313A (en) * 1966-09-07 1969-07-29 Nasa High resolution developing of photosensitive resists
US3622365A (en) * 1968-04-18 1971-11-23 Fairchild Camera Instr Co Process of forming an arsenic sulfide mask
US4133685A (en) * 1969-05-29 1979-01-09 Richardson Chemical Company Lithographic plate and photoresist having photosensitive layers of diazo and cinnamoylated polyvinyl alcohol materials
US4486526A (en) * 1969-05-29 1984-12-04 Richardson Graphics Company Lithographic plate and photoresist having photosensitive layers of diazo and cinnamoylated phenol-blocked isocyanate polyurethane materials
US3808004A (en) * 1969-05-29 1974-04-30 Richardson Graphic Co Lithographic plate and photoresist having two photosensitive layers
US4330611A (en) * 1969-05-29 1982-05-18 Richardson Graphics Company Lithographic plate and photoresist having photosensitive layers of diazo and cinnamoylated polyvinyl alcohol materials
US3640765A (en) * 1969-08-06 1972-02-08 Rca Corp Selective deposition of metal
US3905815A (en) * 1971-12-17 1975-09-16 Minnesota Mining & Mfg Photopolymerizable sheet material with diazo resin layer
US3751248A (en) * 1971-12-27 1973-08-07 Bell Telephone Labor Inc Method of selective multilayered etching
US3883352A (en) * 1973-04-05 1975-05-13 Grace W R & Co Process for forming a photocured solder resist
DE2950212A1 (de) * 1978-12-15 1980-06-19 Fujitsu Ltd Negative tiefultraviolette abdeckung und verfahren zum herstellen eines abdeckungsmusters
US4687727A (en) * 1982-09-21 1987-08-18 Fuji Photo Film Co., Ltd. Light-sensitive planographic printing plate with layer of diazo resin containing photopolymerizable composition
DE3246403A1 (de) * 1982-12-15 1984-06-20 Merck Patent Gmbh, 6100 Darmstadt Verfahren zur entwicklung von reliefstrukturen auf der basis von strahlungsvernetzten polymervorstufen hochwaermebestaendiger polymere
US4539288A (en) * 1982-12-15 1985-09-03 Merck Patent Gesellschaft Mit Beschrankter Haftung Process for the development of relief structures based on radiation-crosslinked polymeric precursors of polymers which are resistant to high temperature
EP0708369A1 (en) 1994-10-11 1996-04-24 Morton International, Inc. Solvent system for forming films of photoimageable compositions

Also Published As

Publication number Publication date
SE340563B (es) 1971-11-22
US3462267A (en) 1969-08-19
CH484458A (de) 1970-01-15
ES342356A1 (es) 1968-07-16

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